JPH0627225B2 - Flame-retardant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition for an electric wire coating sheath.

2. Description of the Related Art Conventional Techniques and Problems Thereof Conventionally known flame-retardant resin compositions are halogen-containing polymers or non-halogen-based polymers to which organic halogen-based flame retardants are added. However, products obtained by using such a flame-retardant resin composition all self-extinguish when they are moved away from the flame, but when they are in a high-temperature flame such as a fire, they burn to the end. However, there are drawbacks such that the resin is continued, smoke is generated, acid gas having strong corrosiveness and toxicity is generated by thermal decomposition, and resin melts and flows.

On the other hand, attempts have been made to eliminate the above-mentioned drawbacks by blending a halogen-free flame retardant with an olefin resin. However, in order to increase the flame retardancy of a resin composition containing a halogen-free flame retardant to a practically sufficient degree, it is necessary to add a large amount of a halogen-free flame retardant, and therefore the following drawbacks Is inevitable.
That is, when a large amount of halogen-free flame retardant is blended with the olefin resin, the molded product of the obtained resin composition is significantly impaired in its mechanical properties, particularly mechanical strength and elongation, aging properties and electrical properties, Inconvenient for practical use. As described above, with respect to the halogen-free resin composition, a flame-retardant resin composition having excellent flame retardancy and capable of imparting practically sufficient mechanical properties and electrical properties to the molded product has not yet been completely developed. The current situation is that it has not been done.

Means for Solving the Problems An object of the present invention is to provide a halogen-free flame-retardant resin composition for a wire-coated sheath that is excellent in flame retardancy.

Another object of the present invention is to provide a resin composition for an electric wire coating sheath, which can impart practically sufficient mechanical properties and electrical properties to the molded product.

Other features of the invention will be apparent from the description below.

The electric wire coating sheath resin composition of the present invention comprises a rubber-like ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 30 to 75% by weight and a Mooney viscosity of 5 to 65 at 100 ° C. Combined 100 parts by weight, (B) magnesium hydroxide and / or aluminum hydroxide 70 to 25
0 parts by weight, (C) general formula Or [In the formula, R represents an alkyl group having 3 to 12 carbon atoms. R '
Represents an alkyl group having 1 to 18 carbon atoms. ] The phosphorus-containing titanate coupling agent represented by
3 parts by weight and 0.1 to 5 parts by weight of (D) a hindered phenol-based and / or amine-based antioxidant.

In the present invention, the polymer component used as the component (A) is a rubber-like ethylene-vinyl acetate copolymer having a vinyl acetate content of 30 to 75% by weight and a Mooney viscosity of 5 to 65 at 100 ° C. It is a united body (hereinafter sometimes referred to as "EVA"), and particularly has a vinyl acetate content of about 40-
A rubbery ethylene-vinyl acetate copolymer having a Mooney viscosity at 100 ° C of about 73% by weight of about 15 to about 40 is preferred. As a specific example, for example, 10
Mooney viscosity at 0 ° C is about 20, vinyl acetate content is 45
Wt% ethylene-vinyl acetate copolymer [Levaprene 4
50, manufactured by Bayer Co., Ltd.], a Mooney viscosity at 100 ° C. of about 20, and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 50% by weight [Levaprene 500, manufactured by Bayer].

In the present invention, ethylene propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-ethyl acrylate copolymer (EEA) and the like may be mixed and used as the component (A) with the above EVA.

As the EPM and EPDM, conventionally known ones can be widely used. A preferred EPM is, for example, a copolymer of ethylene and propylene having a propylene content of about 15 to about 70 mol%, preferably about 20 to about 50 mol%. Also preferred EPD
Examples of M include ethylene and propylene, and a third
An ethylene-propylene-diene terpolymer obtained by copolymerizing dichloropentadiene, ethylidene norbornene, 1,4-hexadiene and the like as a component, wherein the amount of the third component represented by iodine value is about 8 to about 25, preferably Is about 9 ~
The raw rubber Mooney has a viscosity of about 30 to about 100, preferably about 30 to about 60. Examples of the EPM or EPDM include EP21,
EP51 [all manufactured by Japan Synthetic Rubber Co., Ltd.], Esplen 3
01, Esplen 501A, Esplen 505 [all manufactured by Sumitomo Chemical Co., Ltd.], EPT4021, EPT1045
[Ijiri is made by Mitsui Petrochemical Co., Ltd.] and the like.

Examples of EEA include MFR of about 0.4 to about 35 and ethyl acrylate (EA) content of about 5 to about 3.
There may be mentioned 0% by weight, preferably M
FR is about 0.5 to about 28 and EA content is about 5
An example is about 20% by weight. Specific examples thereof include NUC-6220, DQDJ-6182,
NUC-6570 [all manufactured by Nippon Unicar Co., Ltd.], A1
70, A270, T4340-16 [all manufactured by Nippon Petrochemical Co., Ltd.], XC-300E, C-400K [all manufactured by Mitsubishi Petrochemical Co., Ltd.] A-701, A-702, A-706,
A-710 [all manufactured by Mitsui-Dyupon Polychemical Co., Ltd.] and the like can be mentioned.

The EVA, EPM, EPDM or EEA is preferably crosslinked. This cross-linked EVA, EPM,
As EPDM or EEA, conventionally known ones can be widely used, and specifically, the above EVA, EPM, EPDM or EEA added with an organic peroxide, and heat treated for crosslinking, the above EVA, EPM, Cross-linking EVA, EPM, EPDM or EE by irradiating EPDM or EEA with an electron beam
Examples thereof include those of A, water-crosslinkable EVA, EPM, EPDM or EEA.

Further, a small amount of linear polyethylene may be mixed with the component (A) of the present invention. Here, the linear polyethylene is a copolymer of olefin and ethylene having 4 to 16 carbon atoms, and has a density of more than 0.90 and 0.9.
An essentially linear polyethylene having an MFR of 6 or less and an MFR of 0.1 to 20. Such linear polyethylene is produced, for example, by the method shown below.

That is, it is produced by polymerizing a mixture of ethylene and olefin having 4 to 16 carbon atoms under low pressure in the presence of a catalyst. As the mixing ratio of ethylene and olefin,
About 3 to about 20 parts by weight of the latter per 100 parts by weight of the former,
It is preferably about 5 to about 10 parts by weight. The catalyst used is, for example, a so-called Philipps catalyst typified by silica, alumina, zirconia, or chromium oxide with silica-alumina as a carrier, and Periodic Table Group IV to Group IV of the elements.
Examples thereof include a Ziegler catalyst produced by a combination of a Group VIII transition metal compound and a Group I to Group IV organometallic compound. Specific examples of the Ziegler catalyst include TiCl ₄ and alkylaluminum (for example, Al ₂ (Et ₃ ) Cl ₃ , Al.
(Et) ₂ Cl, AlEt ₃ etc.) can be exemplified. Furthermore, a three-way mixture of such organomagnesium compounds of _{n-Bu 2 Mg · 1 /} 6AlEt 3 and said Ti compound and an organic metal halide may be used as a catalyst. The amount of such a catalyst used is ethylene and a carbon number of 4 to 16
Usually about 0.0 per 100 parts by weight of a mixture with olefin.
1 to about 50 parts by weight, preferably about 0.05 to about 20 parts by weight. The pressure during this polymerization is usually about normal pressure to about 20 atm, preferably about normal pressure to about 10 atm. Specific preferred methods for producing these linear polyethylenes include JP-A-51-112891, JP-A-55-45722, and JP-A-55-11.
The methods described in Japanese Patent No. 3542, US Pat. No. 3,957,448 and the like can be exemplified.

In the present invention, among the above linear polyethylene,
Olefin having a carbon number of about 4 to 10 as a comonomer copolymerized with an ethylene chain constituting the polyethylene is preferable, and more specifically, the comonomers are butene-1, octene-1 and 4-methylpentene-. 1 is most preferred. Among the above linear polyethylene, A
The density measured by STM D1505 is preferably about 0.91 to about 0.96, more preferably about 0.91 to about 0.94, most preferably about 0.911 to about 0.925. . Furthermore, among the above linear polyethylenes, the MFR measured by ASTM D1238 is about 0.1.
~ About 10 are preferred. Specific examples of such linear polyethylene include Mitsubishi Polyethylene-LL H20.
E, F30F, F30H (all manufactured by Mitsubishi Petrochemical Co., Ltd.), Ultox 2020L, 3010F, 3021F (all manufactured by Mitsui Petrochemical Co., Ltd.), DFDA-7540 (Union Carbide Co., Ltd.), NUCG-5651, GS-6.
50, GRSN-7047, GRSN-7042 [all manufactured by Nippon Unicar], Idemitsu Polyethylene-L 01
34H and 0234H (both manufactured by Idemitsu Petrochemical Co., Ltd.) can be exemplified.

The amount of the linear polyethylene used by being mixed in the component (A) is usually about 18% by weight or less, preferably about 15% by weight or less based on the total amount of the component (A).

The component (B) in the present invention is magnesium hydroxide and / or
Or it is aluminum hydroxide. Magnesium hydroxide is specifically MgO.nH ₂ O (n is 0.5 to 5, particularly 1.5 to 2.5) (hereinafter referred to as “hydrated magnesia”), and aluminum hydroxide is specifically Al ₂ O
₃ · nH ₂ O (n is 0.5 to 6, especially 2.5 to 3.5) (hereinafter referred to as “hydrated alumina”). In the present invention, these may be used alone or in combination of two or more. The particle size of these hydrates is usually about 10 μm.
The following is particularly suitable, and it is preferably about 5 μm or less, and practically about 0.1 to about 5 μm. Specific examples of hydrated alumina include Hydilite H-42M (manufactured by Showa Light Metal Co., Ltd.), B1403, B1403S (all manufactured by Nippon Light Metal Co., Ltd.). As hydrated magnesia,
Particularly, those having a specific surface area of 3 to 15 m ² / g according to the BET method and having a particle size distribution of 5 μm or more according to the Luzexs method of 0% are preferable. Specific examples thereof include Kisuma 5B, Kisuma 5A, Kisuma 5E (all manufactured by Kyowa Chemical Industry Co., Ltd.), KX-4S (manufactured by Asahi Glass Co., Ltd.) and the like.

In the present invention, the component (B) is usually added in an amount of about 70 to about 250 parts by weight, preferably about 80 to about 200 parts by weight, per 100 parts by weight of the component (A). If the blending amount of the component (B) is too large, the mechanical properties of the obtained resin composition will be deteriorated. On the contrary, if the amount of the component (B) is too small, the flame retardancy of the obtained resin composition will decrease.

In the present invention, the phosphorus-containing titanate coupling agent used as the component (C) has the general formula Or [In formula, R shows a C3-C12 alkyl group. R '
Represents an alkyl group having 1 to 18 carbon atoms. ] It is an organic titanate represented by. Specific examples thereof include tetraisopropyldi (dioctylphosphite) titanate [KR-41B, manufactured by Kenritsu Co.], tetraoctyldi (ditridecylphosphite) titanate [KR-46.
B, manufactured by the same company] Tetraisopropyldi (dilaurylphosphite) titanate [KR-36C, manufactured by the same company], tetra (2,2-diallyloxymethyl-1-butoxy)
Di (di-tridecyl) phosphite titanate [KR-
55, same company], isopropyl tris (dioctylpyrophosphate) titanate [KR-38S, same company], bis (dioctylpyrophosphate) oxyacetate titanate [KR-138S, same company], bis (dioctylpyrophosphate) Examples thereof include ethylene titanate [KR-238S, manufactured by the same company]. Among these, particularly tetraisopropyldi (dioctylphosphite) titanate, tetraisopropyldi (dilaurylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butoxy) di (di-tridecyl)
Phosphite titanate, isopropyl tris (dioctylpyrophosphate) titanate and bis (dioctylpyrophosphate) oxyacetate titanate are preferred.

In the present invention, the phosphorus-containing titanate coupling agent is preferably added in an amount of usually about 0.2 to about 3 parts by weight per 100 parts by weight of the component (A). If the compounding amount of the coupling agent is too large, there is a drawback that properties such as flame retardancy and mechanical properties of the resulting composition deteriorate. On the contrary, if the amount of the coupling agent is too small, the processability of the obtained composition will be deteriorated.

In the present invention, it is necessary to blend an antiaging agent in the composition of the present invention. The anti-aging agent used is a hindered phenol anti-aging agent and / or an amine anti-aging agent. As a hindered phenol anti-aging agent,
A wide variety of known compounds can be used, for example, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate [methane [Irganox 1010, manufactured by Ciba-Geigy], 2,2-thio [ Diethyl-bis-3- (3,5-di-tert-butyl-4-
Hydroxyphenol) propionate] [Irganox 1035, manufactured by Ciba Geigy], 4,4'-thiobis (3-methyl-6-tert-butylphenol) [Santonox, manufactured by Monsanto], 4,4'-methylene-
Examples thereof include bis (3,5-di-tert-butylphenol) [Ionox 220, manufactured by British ICI]. As the amine antiaging agent, conventionally known ones can be widely used, and specific examples thereof include antioxidant DDA [DDA, manufactured by Bayer Co.], N, N′-di-β-naphthyl-p-phenylene. Diamine [Nocrack White, Ouchi Shinko Co., Ltd.], N, N'-diphenyl-p
-Phenylenediamine [Nocrac DP, manufactured by Ouchi Shinko Co., Ltd.], N, N'-diisopropyl-p-phenylenediamine [Antioxidant No. 23, manufactured by DuPont],
N, N'-bis (1-methyl-heptyl) -p-phenylenediamine [Eastman Chem., Eastzone 30],
Phenyl, hexyl-p-phenylenediamine [Pennwa
lt, ANTO ₃ “E”], N, N′-bis (1-ethyl, 3-methylpentyl) -p-phenylenediamine [Uniroyal, Flexzon 8-L], N, N′-di- β
-Naphthyl-p-phenylenediamine [manufactured by Seiko Chemical Co.,
Nonflex F], 2-mercaptomethylbenzimidazole [manufactured by Ouchi Shinko Co., Ltd., Nokurac MMB], 2-mercaptomethylbenzimidazole zinc salt [manufactured by Ouchi Shinkosha,
Nocrack MMBZ] and the like. In the present invention, these antioxidants can be used alone or in combination of two or more.

The amount of the antioxidant to be added is usually about 0.1 to about 5 parts by weight, preferably about 0.2 to about 2.5 parts by weight, more preferably about 0.1 part by weight per 100 parts by weight of the component (A). 3 to about 1.5 parts by weight is recommended. The amount of antioxidant added is 5
Even if it exceeds the amount by weight, the effect of preventing aging does not improve so much, which is economically unfavorable. On the contrary, the amount of the antioxidant added is 0.
If the amount is less than 1 part by weight, it is difficult to exert the antiaging effect, which is not preferable.

In the present invention, red phosphorus, zinc borate as a flame retardant aid,
It is preferable to incorporate titanium dioxide or the like into the composition of the present invention. Here, as the red phosphorus, those commercially available in the past can be widely used. For example, the red phosphorus content is about 80% or more, the loss on drying is about 0.8% or less, and the 74 mesh sieve residue is about 7%. The following are preferable. Further, it is preferable that the surface of the red phosphorus is coated with a thermosetting resin such as a phenol-formalin resin. Specific examples thereof include Novaret # 120 and Novaret # 120UF (both manufactured by Rin Kagaku Kogyo Co., Ltd.).

As the zinc borate, those which are commercially available can be widely used. For example, the chemical formula 2ZnO.3B ₂ O ₃ .3.5H ₂ can be used.
Preferred are those represented by O having a particle size of about 2 to about 10 µ and a crystal density of about 2.6 to about 2.8 g / cm ³ . Specific examples thereof include zinc borate 2335 [Borax, United Kingdom]
Manufactured by the company] and the like.

As the titanium dioxide, those commercially available in the past can be widely used, for example, titanium dioxide containing at least about 90% or more of TiO _{2 and} having a particle size of 100 mesh sieves,
Preferable examples include those containing at least about 90% or more TiO _{2 and} having a 149μ sieve residue of 0% and a water content of about 0.7% or less. More specifically, Tietone A-15
0, Tytone R-650 [all manufactured by Sakai Chemical Industry]
Etc.

In the present invention, these flame retardant aids are usually blended in an amount of about 0.5 to about 50 parts by weight, preferably about 2 to about 25 parts by weight, per 100 parts by weight of the component (A). 50% flame retardant aid
If it exceeds the weight part, the mechanical properties of the obtained resin composition tend to be deteriorated, which is not preferable. On the contrary, if the amount of the flame retardant aid is less than 0.5 parts by weight, the effect of adding the flame retardant aid tends to be unrecognized, which is not preferable.

In the present invention, a silane coupling agent may be further added to the composition of the present invention. The silane coupling agent is preferably a trialkoxysilane having a carbon-carbon double bond or an epoxy group, specifically vinyl-
Tris (β-methoxyethoxysilane) [A172, manufactured by Nippon Unicar], γ-methacryloxypropyltrimethoxysilane [A174, manufactured by the same company], β- (3,4-
Examples thereof include epoxycyclohexyl) ethyltrimethoxysilane [A186, manufactured by the same company], γ-glycidyl oxypropyltrimethoxysilane [SH6040, manufactured by Toray Silicone Company]. Among these, γ-methacryloxypropyltrimethoxysilane is particularly preferable.

The amount of the silane coupling agent is usually about 0.1 to about 5 parts by weight, preferably about 0.3 to about 3 parts by weight, and more preferably about 0.1 part by weight per 100 parts by weight of the component (A).
It is recommended to use 3 to about 2 parts by weight. If the amount of the coupling agent is more than 5 parts by weight, the flame retardancy, heat resistance and the like of the obtained resin composition tend to decrease, which is not preferable.
If the amount of the coupling agent is less than 0.1 part by weight, workability tends to be poor.

In the present invention, it is desirable to incorporate an organic peroxide in the composition of the present invention for crosslinking. As the organic peroxide, conventionally known ones can be widely used, for example, tert-
Butyl cumyl peroxide [Kayabutyl C, Kayaku Nouri Co.], α, α'-bis (tert-butylperoxy-
m-isopropylbenzene) [Perbutyl P, NOF Corporation], 2,5-dimethyl-2,5-di-tert-butylperoxy) hexyne [Perhexa 25B, NOF Corporation], dicumyl peroxide [Perkmill] D, manufactured by NOF CORPORATION, etc. Among these, especially te
rt-Butyl cumyl peroxide, α, α'-bis (tert
-Butylperoxy-m-isopropylbenzene and dicumyl-oxide are preferred.

The amount of the organic peroxide to be blended is usually about 1 to about 10 parts by weight, preferably about 1.5 to about 5 parts by weight, per 100 parts by weight of the component (A). When the compounding amount of the organic peroxide exceeds 10 parts by weight, physical properties such as mechanical properties and aging properties of the resulting composition tend to deteriorate, which is not preferable. If the amount of the organic peroxide is less than 1 part by weight, the crosslinking effect is hard to be recognized, which is not preferable.

Further, it is preferable to add a crosslinking aid to the composition of the present invention. As the crosslinking aid, conventionally known compounds can be widely used as long as they are compounds having at least two reactive carbon-carbon double bond-containing groups in the molecule, and specifically, divinylbenzene, diallyl phthalate, Diallyl isophthalate, 4,4'-isopropylidene diphenol-bis (diethylene glycol methacrylate) ether,
Aromatic polyfunctional compounds such as triallyl trimertate, 2,2'-bis (4-acryloxydiethoxyphenyl) propane, syn-1,2-polybutadiene, 1,4
-Butanediol diacrylate, N, N'-methylenebisacrylamide, ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tritimerolpropane trimethacrylate, pentaerythritol tetramethacrylate, 1,6-hexanediol diacrylate, diethylene glycol dimethacrylate , Triethylene glycol dimethacrylate,
Aliphatic polyfunctional compounds such as 1,6-hexanediol dimethacrylate and tetrahexanediol dimethacrylate, triallyl isocyanurate, triallyl cyanurate, triacryloyl hexahydro-1,3,5-
Includes aliphatic polyfunctional cyclic compounds such as triazine and diacrylic chlorendate, aluminum acrylate, aluminum methacrylate, zinc acrylate, zinc methacrylate, magnesium acrylate, magnesium methacrylate, calcium acrylate, calcium methacrylate, zircon acrylate, zircon methacrylate. Examples thereof include metal polyfunctional compounds. Among these, triallyl isocyanurate, triallyl cyanurate, triacryloyl hexahydro-1,
3,5-triazine and the like are particularly suitable.

The amount of the crosslinking aid compounded in the composition of the present invention is usually about 0.1 to about 10 parts by weight, preferably about 0.3 to about 5 parts by weight, per 100 parts by weight of the component (A). Is good. If the blending amount of the crosslinking aid is more than 10 parts by weight, the mechanical properties and aging properties of the obtained resin composition tend to deteriorate, which is not preferable. On the contrary, if the amount of the crosslinking aid is less than 0.1 parts by weight, the effect of adding the crosslinking aid will not be recognized, which is not preferable.

It is desirable to further add a filler to the composition of the present invention. As the filler, conventionally known ones can be widely used,
For example, talc such as Mistron vapor talc, metal carbonates such as magnesium carbonate and calcium carbonate, zinc oxide,
Examples thereof include metal oxides such as magnesium oxide, beryllium oxide, boron oxide and aluminum oxide, clay, anhydrous silica, graphite, graphite, barium sulfate and lithopone. Of these, clay, mistron vapor talc and magnesium carbonate are particularly preferable.

The amount of such a filler to be added is usually the above-mentioned component (A) 1
About 5 to about 200 parts by weight, preferably about 1 per 100 parts by weight
The amount is preferably 0 to about 150 parts by weight, more preferably about 5 to about 50 parts by weight. When the blending amount of the filler exceeds 200 parts by weight, the mechanical properties of the obtained resin composition tend to deteriorate, which is not preferable. Further, if the amount of the filler to be blended is less than 5 parts by weight, the effect of adding the filler cannot be recognized, which is not preferable.

The composition of the present invention preferably contains a higher fatty acid or a metal salt thereof as a processing aid. Examples of higher fatty acids include stearic acid and oleic acid, and examples of metal salts include zinc salts and calcium salts.

The amount of the higher fatty acid or metal salt thereof to be added is usually about 0.1 to about 10 parts by weight, preferably about 0.5 to about 5 parts by weight, per 100 parts by weight of the component (A).
If the blending amount of the higher fatty acid or its metal salt exceeds 10 parts by weight, there is a tendency that the resin composition obtained has a drawback that properties such as mechanical properties are deteriorated. If the blending amount is less than 0.1 part by weight, the effect of addition as a processing aid cannot be recognized.

It is preferable to further incorporate a copper damage inhibitor into the composition of the present invention. As the copper damage inhibitor to be used, conventionally known ones can be widely used, for example, N, N'-bis (3-
(3 ', 5'-di-tert-butyl-4'hydroxyphenyl) propionyl) hydrazine, (3- (N-salicyloyl) amino-1,2,4-tetrazole), N,
Examples thereof include N'-dibenzal oxalyl hydrazide and N, N'-disalicylidene oxalyl hydrazide. The compounding amount of the copper damage inhibitor is usually about 0.02 to about 5 parts by weight, preferably about 0.1 to 100 parts by weight of the component (A).
It is recommended to use about 2 parts by weight. Even if the content of the copper damage inhibitor exceeds 5 parts by weight, the effect of addition of the copper damage inhibitor is not so improved, which is economically unfavorable. Further, if the content of the copper damage inhibitor is less than 0.02 part by weight, the copper damage preventing effect is difficult to be exhibited.

Further, it is preferable to add carbon black to the composition of the present invention. As the carbon black, conventionally known ones can be widely used. Among them, a preferable one is, for example, a DBP oil absorption of 100 to 160 cm.
³ / 100g with ASTM code N330-N3
Recognized Sulfur ness wanders as 51, DBP oil absorption amount can be exemplified a thermal wander like of 30 to 50 cm ^3/100 g. Specific examples of such carbon black include FEF carbon black, HAF carbon black, ISAF carbon black, SRF carbon black, and the like. More specifically, for example, diamond black H, diamond black HS (all are Mitsubishi Kasei Made], V
ulcan-3, Vulcan-3H [all manufactured by KYABOT CORPORATION], SEAST H, SEAST 3H [all manufactured by Tokai Electrode], Ketsutsu Embrack HAF [manufactured by Ketsutsuen] and the like. Among these, diamond black H and Vulcan-3 are preferable.

In the present invention, the above carbon black is usually used as the component (A) 1
About 0.5 to about 200 parts by weight, preferably about 0.5 to about 40 parts by weight, more preferably about 1 to about 20 parts by weight per 00 parts by weight.
It is preferable to use parts by weight. The amount of carbon black is 2
If it exceeds 100 parts by weight, mechanical properties of the obtained resin composition tend to be impaired, which is not preferable. If the amount of carbon black is less than 0.5 part by weight, the ashing characteristics are difficult to be exhibited, which is not preferable.

In addition to the above-mentioned various components, various plasticizers, pigments and the like can be added to the composition of the present invention. The tendency arises.

Examples of the plasticizer include naphthene-based, aroma-based, process oil, phthalic acid esters, trimellitic acid esters, epoxy resins and the like, and the compounding amount thereof is usually about 0 per 100 parts by weight of the component (A). .2 to about 50
The amount is preferably about 1 to about 10 parts by weight.

Examples of the pigment include phthalocyanine blue, chrome yellow, red iron oxide, and the like, and the compounding amount thereof is usually about 1.0 to about 20 per 100 parts by weight of the component (A).
It is preferable that the amount is about 5 parts by weight, preferably about 5 to about 10 parts by weight.

The resin composition of the present invention can be used after being crosslinked.
Examples of the crosslinking method in this case include a method using an organic peroxide, a crosslinking method using an electron beam, a crosslinking method using radiation, and a method using water crosslinking.

The composition of the present invention can be obtained by appropriately mixing the predetermined amounts of the above-mentioned various components and uniformly mixing them by a conventionally known method using a Banbury mixer, a Henschel mixer or the like. All of the above components can be mixed at the same time, but the coupling agent is preferably added at the same time when the filler is added. When two or more polymers are used as the component (A), it is preferable that the polymers are first mixed uniformly and then the other components are mixed.

In using the composition of the present invention, various conventionally known molding methods can be widely adopted. For example, the composition of the present invention is kneaded using a kneader such as a roll kneader, and then this is used depending on the application. And may be formed into various shapes.

EFFECTS OF THE INVENTION The composition of the present invention is essentially halogen-free, so that even when it is left in a flame at high temperature such as in the case of a fire, smoke is generated, and a corrosive gas is generated due to thermal decomposition. It does not generate acid gas and has excellent flame retardancy, mechanical strength, electrical characteristics, aging resistance and the like. Therefore, the composition of the present invention, building materials, pipes, hoses,
It is suitable as a covering material for sheets, seat covers, wall materials, electric cables (inner insulators, outer sheaths, etc.).

In particular, the composition of the present invention can be suitably used as a flame-retardant resin composition for insulating coating or sheath coating of electric cables. In such a case, the composition of the present invention is used as an electrical insulating layer on a conductor of various communication cables, power cables, control cables and the like, on an appropriate portion such as on an inner semiconductive layer, and on the insulating layer of these cables. , Can be used as a protective layer (sheath) on an appropriate portion such as on the outer semiconductive layer, and in any of these cases, the electric wire cable can be imparted with high flame retardancy and flame resistance.

Examples The present invention will be further clarified with reference to the following examples.

The characteristics of the samples obtained in the following examples were tested by the following methods.

<Flame retardancy test> The composition of the present invention (No. 1 to 5) and the comparative composition (No. 6)
Is kneaded with two rolls at 160 ° C for 20 minutes, then 170 ° C
A sample sheet having a thickness of 3.0 mm is prepared by press molding for 10 minutes, and the sample sheet is irradiated with an electron beam of 15 Mrads in the air using a Diatron DP1000 type electron beam accelerator to cross-link, and then JIS. The oxygen index (LOI) is determined according to K7201 (oxygen index method) to evaluate the flame retardancy.

<Mechanical properties> Kneading and molding are performed in the same manner as described above to prepare a sample sheet having a thickness of 1 mm, and the properties of the sample sheet are examined.

(1) 100% module (kg / mm ² ) According to ASTM D882.

(2) 200% module (kg / mm ² ) According to ASTM D882.

(3) Tensile strength (kg / mm ² ) According to ASTM D882.

(4) Elongation (%) According to ASTM D882. The composition of the present invention No. 1
In No. 8, it was measured by an autograph according to JIS K6301 vulcanized rubber test method. And, those of 150% or more are evaluated as ◯ and those of 150% or less are evaluated as x.

<Gel Fraction (%)> For the same sample sheet used in the above flame retardancy test, A
Measure according to STM D2765.

<Electrical Properties> A sample sheet having a thickness of 1 mm prepared by the same molding and crosslinking method as the sample sheet used in the flame retardancy test was used. For these sample sheets, ρ (oh
m-cm).

<Aging property> For the same sample sheet used in the above electrical property test,
According to ASTM D573, tensile strength residual rate (%) and elongation residual rate (%) after 150 ° C. × 4 days are determined.

Further, the symbols of the respective components in the following respective examples show the following.

<Base polymer> A-1 ... EVA [manufactured by Bayer Co., Levaprene 450, V
A content = 45% by weight] A-2 ... EVA [manufactured by Bayer Co., Levaprene 500, V
A content = 50% by weight] <Flame retardant> B-1 ... Mg (OH) ₂ [Kyowa Chemical Co., Kisuma 5B] <Coupling agent> C-1 ... Tetra (2,2-diallyloxymethyl-1-)
Butoxy) di (di-tridecyl) phosphite titanate [manufactured by Kenrich Co., [KR-55] C-2 ... Isopropyl-triisostearoyl titanate [manufactured by Ajinomoto Co., Plainact] <Antiaging Agent> D-1 ... Tetrakis [ Methylene-3- (3,5-di-te
rt-Butyl-4-hydroxyphenyl) propionate] methane [manufactured by Ciba Geigy, Irganox 101]
0] <Additive> E-1 ... Stearic acid E-2 ... Zinc stearate E-3 ... Copper damage inhibitor [MARK manufactured by ADEKA ARGUS CORPORATION, MARK]
CDA-1] E-4 ... HAF carbon [manufactured by Mitsubishi Kasei], Diamond Black H] E-5 ... Seanox 412S [manufactured by Shiraishi Calcium Co.] Examples and Comparative Examples Base polymers and flame retardants shown in Table 1 below. A composition of the present invention and a comparative composition were obtained by mixing predetermined amounts (parts by weight) of a phosphorus-containing titanate coupling agent, an antioxidant and other additives.

Physical properties of the composition of the present invention and the comparative composition obtained above are shown in Table 2 below.

The sheet obtained by using the composition of the present invention in which the phosphorus-containing titanate coupling agent is blended from Table 2 above is a sheet obtained by using the comparative composition in which the phosphorus-containing titanate coupling agent is not blended. In comparison, it can be seen that it is superior in electrical properties, mechanical properties and flame retardancy.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08K 3:22 5:52 5: 3435 5:13) (56) Reference JP-A 61-213240 (JP, A) JP 61-106646 (JP, A) JP 55-31871 (JP, A) JP 59-179538 (JP, A) JP 61-31446 (JP, A) Kohei 5-17934 (JP, B2)

Claims (1)

[Claims] 1. A vinyl acetate content of (A) is 30 to 75% by weight.
And 100 to 100 parts by weight of a rubber-like ethylene-vinyl acetate copolymer having a Mooney viscosity of 5 to 65 at 100 ° C., (B) 70 to 250 parts by weight of magnesium hydroxide and / or aluminum hydroxide, (C ) General formula Or [In the formula, R represents an alkyl group having 3 to 12 carbon atoms. R '
Represents an alkyl group having 1 to 18 carbon atoms. ] The phosphorus-containing titanate coupling agent represented by
A flame-retardant resin composition for an electric wire coating sheath, which comprises 3 parts by weight and 0.1 to 5 parts by weight of (D) a hindered phenol-based and / or amine-based antioxidant.